US5248716A - Silicone pressure-sensitive adhesives with control removal property - Google Patents
Silicone pressure-sensitive adhesives with control removal property Download PDFInfo
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- US5248716A US5248716A US07/828,437 US82843792A US5248716A US 5248716 A US5248716 A US 5248716A US 82843792 A US82843792 A US 82843792A US 5248716 A US5248716 A US 5248716A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
Definitions
- Solventless and high solids silicone pressure sensitive adhesives provide excellent cure, peel and tack adhesion properties on polyester, polyimide, and polytetrafluoroethylene tapes.
- some cured PSA tapes have a high affinity to the back side of adhesive tapes. This affinity is undesirable since it leads to difficulties in unwinding and slitting operations and inconsistency in tape appearance upon dispensing. This phenomenon is most apparent with adhesives having a polyester backing.
- compositions which are curable to produce pressure sensitive adhesives, display this high affinity to the backside of adhesive tapes.
- these compositions include recently developed solventless or low solvent-containing organopolysiloxane compositions which comprise by weight: (A) from about 50 to about 75 parts by weight of a toluene and benzene soluble, resinous copolymer comprising R 3 SiO 1/2 units and SiO 4/2 units wherein R is a monovalent hydrocarbon radical having from 1 to 6 carbon atoms; (B) an alkenyl-terminated polydiorganosiloxane; (C) an organohydrogenpolysiloxane compatible with the mixture of (A) and (B); (D) a catalytic amount of a hydrosilation catalyst; and (E) from 0 to about 40% by weight of an organic solvent.
- organopolysiloxane compositions which comprise by weight: (A) from about 50 to about 75 parts by weight of a toluene and benzene
- compositions having such high backside affinities include compositions of the type described above which further comprise a hydrogen-containing polydiorganosiloxane containing more than two silicon-bonded hydrogen atoms per chain and being present in an amount such that (D) has a silicon-bonded hydrogen content of from about 10 to about 100 mole % based on the total silicon-bonded hydrogen content of (C) and (D).
- the dispensing angle affects the surface smoothness and optical quality of the removed tapes.
- a substantially clear, smooth undistorted adhesive tape can be obtained.
- a more common dispensing angle a relatively hazy, roughened tape is obtained.
- silicone pressure sensitive adhesives which can be dispensed with little caution using available equipment and settings and still obtain a smooth surface and minimal distorted optical characteristics.
- distortion and haze upon removal can be minimized by incorporating a small amount of chemically compatible, high molecular weight silicone polymer release modifier to the curable PSA compositions discussed above.
- the clean and smooth removal properties of the cured silicone PSA tapes can be adjusted by choosing the type and amount of release modifier in the curable silicone pressure-sensitive compositions.
- a useful control removal additive According to another embodiment of the present invention, a useful control removal additive
- a) is chemically miscible with curable compositions of MQ resin/hydride systems and vinyl fluids and/or cross-linker
- the organopolysiloxanes of the present invention are useful as release modifiers and are effective in compositions suitable for forming a pressure-sensitive adhesive.
- the release modifier minimizes distortion and roughening of the cured silicone PSA surface upon removal (unwinding) or dispensing.
- Useful organopolysiloxanes of the present invention have the general formula:
- each R 1 and R 2 is independently an aryl or alkyl group having from 1 to about 10 carbon atoms, each R is independently chosen from the following groups: R 1 , R 2 , alkenyl having from 1 to about 10 carbon atoms, hydrogen, alkoxy (such as methoxy, ethoxy, propoxy, etc.) hydroxy, epoxy, amino, and fluorochemicals having up to 10 carbon atoms such as partially or fully fluorinated alkyl, alkenyl, ether or ester groups comprising from 1 to about 8 carbon atoms attaching directly to backbone silicon atoms or attaching indirectly to backbone silicon atoms through an organosiloxane segment containing from 1 to about 10 silicon atoms; x and y are each an integer such that the value of (x+y) is sufficient to yield a composition having a viscosity of from at least 1500 cps at room temperature to as high as the viscosity of silicone gums, preferably a viscosity of 10,000
- compositions expressed in the above formula can be identified structurally as homopolymers, or copolymers of random, alternating or block chain structures consisting of the repeating units.
- the compositions should be chemically miscible with the mixture of MQ resin, silicone fluids and polymers as taught in the prior art.
- One particular example is a silanol-stopped poly(dimethylsiloxane) gum of about 8.6 million cps viscosity which was shown to also be reasonably effective.
- This control removal additive organopolysiloxane was found to be effective in compositions as described in the Background of the Invention, particularly those having from about 50 to about 75 parts of a benzenesoluble silicone resin and about 25 to about 50 parts of vinyl- and hydride-containing organopolysiloxanes.
- the weight percentage of the control removal additive organopolysiloxane is based upon 100 parts by weight of the resin and the vinyl- or hydride-containing organopolysiloxane mixture
- the compositions further include a Pt-catalyst, and from 0 to 40 weight percent organic solvent.
- organopolysiloxanes were also found to be effective in compositions as described in the Background of the Invention, particularly those curable compositions having relatively low viscosity at high solids or solventless state, for example, a viscosity of 200,000 cps at 25° C. at 94% solid.
- organopolysiloxanes as release modifiers does not depend on a particular type of curing reaction or mechanism leading to useful adhesive matrix, nor does it depend on particular curing conditions such as cure temperature or cure time, so long as a satisfactory cure is achieved. It is not critical whether curing reaction is an addition reaction between silicon hydride and alkenyls of silicones or condensation reactions between silanol group and silicon hydride or among silanol groups contained within.
- High solid's (e.g. 95%) mixtures curable to form silicone pressure-sensitive adhesives were prepared comprising MQ resin having the units R 3 SiO 1/2 (or M) and SiO 2 (or Q) at a ratio of about 0.7, and about 2 weight percent of silicon-bonded hydroxy group.
- Component A comprised 58 weight percent MQ resin and 42 weight percent fluid made by mixing 279 gms of an MQ resin which is 60% solid in 40% toluene by weight, with 121 gms of vinyl-stopped dimethylsilicone (M"D 105 M") fluid, and 0.40 gms of Kardstadt Pt-catalyst (5% Pt). The mixture was then vacuum stripped to remove toluene solvent to obtain 95% solid or solventless mixture.
- Component B was made to a weight ratio of 58 weight percent MQ resin to 42 weight percent hydride-stopped M H D 121 M H silicone fluid by mixing 193 gms of the 60% solids MQ resin with 84 gms of the hydride stopped silicone fluid The volatile solvent was then removed through a vacuum stripper at a temperature of 70° C. or less. Then, 1.77 gms of dimethyl maleate inhibitor and 2.77 gms of a methylhydrogen silicone fluid of the approximate structure, M H D 20 D H 3 M H , having a hydride equivalent weight (HEW) of 625 was added. The resultant Component B had an averaged HEW of 3796.
- a composition without having any modifier was prepared by mixing 10.0 gms of Component A, shown in Example 1, with 14.25 gms of Component B, shown in Example 1, along with 0.60 gms of the M H D 121 M H hydride fluid, and 0.6 gms of the M"D 105 M" vinyl fluid. This yielded a weight percent ratio of 55.1 MQ to 44.9 fluids and a SiH to SiVinyl ratio of 1.498.
- the composition was coated with a wire-wound rod over a clear 1 mil polyester film, then cured for 3 minutes at 150° C.
- the cured silicone adhesive was 2.0 mil thick and had a Polyken tack adhesion of 616 gms/cm, and a peel adhesion of 33 oz/in against the steel plate.
- the haze after release at 90° was 24.2%, and 3.0% at 180° removal angle. These values are considered high for adhesive applications requiring good optics and finish.
- a dimethylvinyl-stopped polydimethylsiloxane polymer of about 85,000 cps viscosity at room temperature was used as a modifier to the basic composition illustrated in Example 1.
- the basic composition mixture is prepared by mixing 10.0 gms of Component A with 14.25 gms of Component B, both shown in Example 1.
- To the total solids of the basic composition (as 100 parts) 5.2 and 9.7 parts by weight of the modifier were added, respectively.
- the final mixture had a SiH (silicon-bonded hydride) to SiV (also known as silicon-bonded vinyl) ratio of about 1.498.
- the base mixture in Example 5 consisted of 10.0 gms of Component A and 12.38 gms of Component B.
- Example 5 3.75 gms of the high viscosity polymer was added to produce 17.7 parts by weight additive per 100 parts by weight of the mixture of Components A and B. From these mixtures Cured silicone adhesive tapes were made on 1 mil polyester film. The corresponding peel, tack adhesion and removal property, in terms of % haze reading at both 90° and 180° angles are shown in Table 1 below Significant reduction in % haze was obtained from the cured tapes.
- Example 6 a series of dimethylhydroxy-stopped polydimethylsiloxanes, of viscosity from 7600 cps to as high as 8.6 ⁇ 10 6 cps at room temperature were used as modifiers.
- a composition without modifier was made by mixing 10 g of Component A with 12.38 gms of Component B, both shown in Example 1.
- Examples 7 through 10 are compositions based on 100 parts by weight of the base composition in Example 6, with 5.6 parts by weight of modifier.
- Cured silicone pressure-sensitive adhesives were made from each of these compositions, according to the procedure in Example 2. All adhesives showed complete cure and no residue upon testing. The test results are shown in Table II.
- the modifier-containing adhesives (Examples 7-10) had reasonable peel and tack adhesion and significant less haze at a 90° peel angle than what was observed in Example 6.
- the % haze readings at 180° peel angle suggest inherent contributions from a particular polyester film and cured adhesive mass.
- a silicone polymer containing epoxide (cyclohexeneoxide as derived from the reaction product of vinylcyclohexeneoxide with siliconhydride) with a viscosity of 1680 cps was used at a ratio of 5.6 parts by weight to a 100 parts by weight solid of the base composition of Example 6.
- a completely cured pressure-sensitive adhesive tape of 1.8 mil thickness was obtained.
- the peel adhesion was 23 oz/in
- Polyken tack was 690 gms/cm
- a haze value of 7.3% was obtained at 90° removal angle.
- silicone modifier of 1600 cps showed some improvement over the one without any modifier in terms of minimizing surface and optics distortion.
- Example 15 The effects of the partial miscibility of the release modifier with the base composition of MQ resin, silicone fluids and/or polymers and Pt-catalyst is shown in these Examples 15 and 16.
- a dimethylhydroxy-stopped fluorosilicone polymer of 100,000 cps viscosity was used at 5.6 parts by weight per 100 parts by weight of the base composition.
- Example 16 a vinyl-stopped copolymer of dimethyl silicone and trifluoropropylmethylsilicone of 29,000 cps was used at 5.6 parts by weight per 100 parts by weight of the base composition.
- the % haze of 90° angle peeled tapes had readings of 9.4 and 12.5, respectively.
- the higher % haze in Example 16 was the result of less chemical miscibility with the base material before cure.
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Abstract
Distortion and haze of pressure sensitive tapes upon removal can be minimized by incorporating a small amount of chemically compatible, high molecular weight silicone polymer release modifier to the curable PSA compositions. Organopolysiloxanes of the general formula:
RR.sup.1.sub.2 SiO(R.sup.1.sub.2 SiO).sub.x (RR.sup.2 SiO).sub.y
SiR1 2 R
are used as the release modifier, wherein each R1 and R2 is independently an aryl or alkyl group having from 1 to about 10 carbon atoms, each R is independently chosen from the following groups: R1, R2, alkenyl having from 1 to about 10 carbon atoms, hydrogen, alkoxy (such as methoxy, ethoxy, propoxy, etc.) hydroxy, epoxy, amino, and fluoroalkyl having up to 10 carbon atoms; x and y are each an integer such that the value of (x+y) is sufficient to yield a composition having a viscosity of from at least 1500 cps at room temperature to as high as the viscosity of silicone gums. When compared to similar compositions without the release modifier, a cured silicone PSA with much less distortion, a smoother surface, and clearer optics is obtained upon removal or dispensing.
Description
This application relates to U.S. application Ser. Nos. 07/675,232, 07/675,380 and 07/675,396, filed on Mar. 26, 1991.
Solventless and high solids silicone pressure sensitive adhesives provide excellent cure, peel and tack adhesion properties on polyester, polyimide, and polytetrafluoroethylene tapes. However, some cured PSA tapes have a high affinity to the back side of adhesive tapes. This affinity is undesirable since it leads to difficulties in unwinding and slitting operations and inconsistency in tape appearance upon dispensing. This phenomenon is most apparent with adhesives having a polyester backing.
Some specific compositions which are curable to produce pressure sensitive adhesives, display this high affinity to the backside of adhesive tapes. In particular, these compositions include recently developed solventless or low solvent-containing organopolysiloxane compositions which comprise by weight: (A) from about 50 to about 75 parts by weight of a toluene and benzene soluble, resinous copolymer comprising R3 SiO1/2 units and SiO4/2 units wherein R is a monovalent hydrocarbon radical having from 1 to 6 carbon atoms; (B) an alkenyl-terminated polydiorganosiloxane; (C) an organohydrogenpolysiloxane compatible with the mixture of (A) and (B); (D) a catalytic amount of a hydrosilation catalyst; and (E) from 0 to about 40% by weight of an organic solvent.
Other specific compositions having such high backside affinities include compositions of the type described above which further comprise a hydrogen-containing polydiorganosiloxane containing more than two silicon-bonded hydrogen atoms per chain and being present in an amount such that (D) has a silicon-bonded hydrogen content of from about 10 to about 100 mole % based on the total silicon-bonded hydrogen content of (C) and (D).
When dispensing tapes having compositions of these types, the dispensing angle affects the surface smoothness and optical quality of the removed tapes. When dispensing a polyester-backed silicone adhesive at 180° angle, a substantially clear, smooth undistorted adhesive tape can be obtained. However, at 90°, a more common dispensing angle, a relatively hazy, roughened tape is obtained. To adhesive tape manufacturers and users, it is desirable to have silicone pressure sensitive adhesives which can be dispensed with little caution using available equipment and settings and still obtain a smooth surface and minimal distorted optical characteristics.
Therefore, it is desirable to develop methods and compositions curable to form silicone adhesives with improved resistance to distortion and haze upon removal from a finished tape roll, regardless of the dispensing angle.
According to the present invention, distortion and haze upon removal can be minimized by incorporating a small amount of chemically compatible, high molecular weight silicone polymer release modifier to the curable PSA compositions discussed above.
When compared to similar compositions without the release modifier, a cured silicone PSA with much less distortion, a smoother surface, and clearer optics is obtained upon removal or dispensing.
According to an embodiment of the present invention, the clean and smooth removal properties of the cured silicone PSA tapes can be adjusted by choosing the type and amount of release modifier in the curable silicone pressure-sensitive compositions.
According to another embodiment of the present invention, a useful control removal additive
a) is chemically miscible with curable compositions of MQ resin/hydride systems and vinyl fluids and/or cross-linker,
b) has a minimal viscosity of 1500 cps at room temperature or an approximate molecular weight of 30,000,
c) does not interfere Pt-catalyzed, addition-cure reaction chemistry, and
d) is stable in the cured pressure-sensitive adhesive compounds.
The organopolysiloxanes of the present invention are useful as release modifiers and are effective in compositions suitable for forming a pressure-sensitive adhesive. About 0.5 to 15 weight percent, preferably 2 to 10 weight percent of modifier, based on the amount of curable PSA composition, can be added to these high solids and solventless curable compositions to facilitate an easy and smooth removal from the backside of an adhesive tape. The release modifier minimizes distortion and roughening of the cured silicone PSA surface upon removal (unwinding) or dispensing.
Useful organopolysiloxanes of the present invention have the general formula:
RR.sup.1.sub.2 SiO(R.sup.1.sub.2 SiO).sub.x (RR.sup.2 SiO).sub.y SiR.sup.1.sub.2 R
wherein each R1 and R2 is independently an aryl or alkyl group having from 1 to about 10 carbon atoms, each R is independently chosen from the following groups: R1, R2, alkenyl having from 1 to about 10 carbon atoms, hydrogen, alkoxy (such as methoxy, ethoxy, propoxy, etc.) hydroxy, epoxy, amino, and fluorochemicals having up to 10 carbon atoms such as partially or fully fluorinated alkyl, alkenyl, ether or ester groups comprising from 1 to about 8 carbon atoms attaching directly to backbone silicon atoms or attaching indirectly to backbone silicon atoms through an organosiloxane segment containing from 1 to about 10 silicon atoms; x and y are each an integer such that the value of (x+y) is sufficient to yield a composition having a viscosity of from at least 1500 cps at room temperature to as high as the viscosity of silicone gums, preferably a viscosity of 10,000 cps or above. Depending upon the types of R and its presence in the chain, compositions expressed in the above formula can be identified structurally as homopolymers, or copolymers of random, alternating or block chain structures consisting of the repeating units. The compositions should be chemically miscible with the mixture of MQ resin, silicone fluids and polymers as taught in the prior art. One particular example is a silanol-stopped poly(dimethylsiloxane) gum of about 8.6 million cps viscosity which was shown to also be reasonably effective.
This control removal additive organopolysiloxane was found to be effective in compositions as described in the Background of the Invention, particularly those having from about 50 to about 75 parts of a benzenesoluble silicone resin and about 25 to about 50 parts of vinyl- and hydride-containing organopolysiloxanes. The weight percentage of the control removal additive organopolysiloxane is based upon 100 parts by weight of the resin and the vinyl- or hydride-containing organopolysiloxane mixture The compositions further include a Pt-catalyst, and from 0 to 40 weight percent organic solvent.
These organopolysiloxanes were also found to be effective in compositions as described in the Background of the Invention, particularly those curable compositions having relatively low viscosity at high solids or solventless state, for example, a viscosity of 200,000 cps at 25° C. at 94% solid.
The effectiveness of organopolysiloxanes as release modifiers does not depend on a particular type of curing reaction or mechanism leading to useful adhesive matrix, nor does it depend on particular curing conditions such as cure temperature or cure time, so long as a satisfactory cure is achieved. It is not critical whether curing reaction is an addition reaction between silicon hydride and alkenyls of silicones or condensation reactions between silanol group and silicon hydride or among silanol groups contained within.
To better describe "control removal" property and its effect on the appearance of a cured PSA property, a method was developed to describe the optics and the smoothness of adhesive tapes. The compositions below were applied over a 1 mil polyester film and cured to form a 1.5 to 2 mil silicone adhesive layer. Then the cured adhesive film was pressed against a cleaned stainless steel plate using a 4.5 pound rubber roll. After 20 minutes, the tape was removed at 90° and 180° angles, respectively, relative to the plate. The removed adhesive tapes were subjected to a % haze measurement using a Gardener colorimeter. The % haze value of the untested adhesive was also measured and used as a standard. The reported % haze is the difference between the tested value and the standard value, which reflects the net change in % haze due to mechanical dispensing or removal. The lower the value, the less distortion and better removal property of a cured adhesive.
High solid's (e.g. 95%) mixtures curable to form silicone pressure-sensitive adhesives were prepared comprising MQ resin having the units R3 SiO1/2 (or M) and SiO2 (or Q) at a ratio of about 0.7, and about 2 weight percent of silicon-bonded hydroxy group. Component A comprised 58 weight percent MQ resin and 42 weight percent fluid made by mixing 279 gms of an MQ resin which is 60% solid in 40% toluene by weight, with 121 gms of vinyl-stopped dimethylsilicone (M"D105 M") fluid, and 0.40 gms of Kardstadt Pt-catalyst (5% Pt). The mixture was then vacuum stripped to remove toluene solvent to obtain 95% solid or solventless mixture.
Similarly, Component B was made to a weight ratio of 58 weight percent MQ resin to 42 weight percent hydride-stopped MH D121 MH silicone fluid by mixing 193 gms of the 60% solids MQ resin with 84 gms of the hydride stopped silicone fluid The volatile solvent was then removed through a vacuum stripper at a temperature of 70° C. or less. Then, 1.77 gms of dimethyl maleate inhibitor and 2.77 gms of a methylhydrogen silicone fluid of the approximate structure, MH D20 DH 3 MH, having a hydride equivalent weight (HEW) of 625 was added. The resultant Component B had an averaged HEW of 3796.
A composition without having any modifier was prepared by mixing 10.0 gms of Component A, shown in Example 1, with 14.25 gms of Component B, shown in Example 1, along with 0.60 gms of the MH D121 MH hydride fluid, and 0.6 gms of the M"D105 M" vinyl fluid. This yielded a weight percent ratio of 55.1 MQ to 44.9 fluids and a SiH to SiVinyl ratio of 1.498.
After thorough mixing, the composition was coated with a wire-wound rod over a clear 1 mil polyester film, then cured for 3 minutes at 150° C. The cured silicone adhesive was 2.0 mil thick and had a Polyken tack adhesion of 616 gms/cm, and a peel adhesion of 33 oz/in against the steel plate. The haze after release at 90° was 24.2%, and 3.0% at 180° removal angle. These values are considered high for adhesive applications requiring good optics and finish.
A dimethylvinyl-stopped polydimethylsiloxane polymer of about 85,000 cps viscosity at room temperature was used as a modifier to the basic composition illustrated in Example 1. For Examples 3 and 4, the basic composition mixture is prepared by mixing 10.0 gms of Component A with 14.25 gms of Component B, both shown in Example 1. To the total solids of the basic composition (as 100 parts) 5.2 and 9.7 parts by weight of the modifier were added, respectively. The final mixture had a SiH (silicon-bonded hydride) to SiV (also known as silicon-bonded vinyl) ratio of about 1.498. The base mixture in Example 5 consisted of 10.0 gms of Component A and 12.38 gms of Component B. In Example 5, 3.75 gms of the high viscosity polymer was added to produce 17.7 parts by weight additive per 100 parts by weight of the mixture of Components A and B. From these mixtures Cured silicone adhesive tapes were made on 1 mil polyester film. The corresponding peel, tack adhesion and removal property, in terms of % haze reading at both 90° and 180° angles are shown in Table 1 below Significant reduction in % haze was obtained from the cured tapes.
TABLE I
__________________________________________________________________________
Weight Release
Release
Experiment
Viscosity
Parts
SiH/SiV
Percent
Probe Tack
Peel (Steel)
at 90° %
at 180° %
Number
of Modifier
Additive
Ratio
MQ gms/cm.sup.2
oz/in Haze Haze
__________________________________________________________________________
2 85 M cps
0 1.498
55.1 616 33 24.2 3
3 85 M cps
5.2 1.498
55.1 656 29 0.9 0.7
4 85 M cps
9.7 1.498
52.9 622 22 1.2 0.8
5 85 M cps
17.7 1.3 49.3 638 19 7.7 1
__________________________________________________________________________
To optimize the viscosity range of useful control removal additives, a series of dimethylhydroxy-stopped polydimethylsiloxanes, of viscosity from 7600 cps to as high as 8.6×106 cps at room temperature were used as modifiers. In Example 6, a composition without modifier was made by mixing 10 g of Component A with 12.38 gms of Component B, both shown in Example 1. Examples 7 through 10 are compositions based on 100 parts by weight of the base composition in Example 6, with 5.6 parts by weight of modifier. Cured silicone pressure-sensitive adhesives were made from each of these compositions, according to the procedure in Example 2. All adhesives showed complete cure and no residue upon testing. The test results are shown in Table II. The modifier-containing adhesives (Examples 7-10) had reasonable peel and tack adhesion and significant less haze at a 90° peel angle than what was observed in Example 6. The % haze readings at 180° peel angle suggest inherent contributions from a particular polyester film and cured adhesive mass.
TABLE II
__________________________________________________________________________
Weight Release
Release
Experiment
Viscosity
Parts
SiH/SiV
Percent
Probe Tack
Peel (Steel)
at 90° %
at 180° %
Number
of Modifier
Additive
Ratio
MQ gms/cm.sup.2
oz/in Haze Haze
__________________________________________________________________________
6 0 1.3 58 704 40 8.5 1.9
7 7600 cps
5.6 1.3 54.9 632 26 3.2 2.1
8 30 M cps
5.6 1.3 54.9 676 26 3.5 1.8
9 130 M cps
5.6 1.3 54.9 684 25 4.6 2.5
10 8.59 MM cps
5.6 1.3 54.9 770 32 5.9 2.6
__________________________________________________________________________
A silicone polymer containing epoxide (cyclohexeneoxide as derived from the reaction product of vinylcyclohexeneoxide with siliconhydride) with a viscosity of 1680 cps was used at a ratio of 5.6 parts by weight to a 100 parts by weight solid of the base composition of Example 6. A completely cured pressure-sensitive adhesive tape of 1.8 mil thickness was obtained. The peel adhesion was 23 oz/in, Polyken tack was 690 gms/cm,, and a haze value of 7.3% was obtained at 90° removal angle. As compared to a reading of 8.5% for Example 6, silicone modifier of 1600 cps showed some improvement over the one without any modifier in terms of minimizing surface and optics distortion.
To illustrate the option of using alkyl-stopped silicone polymers (up to 18 carbon atoms) as release modifiers, a polydimethylsiloxane polymer of 100,000 cps viscosity was used at 0.99, 2.8, and 5.6 parts by weight per 100 parts by weight solid of the base composition in Example 6. All compositions were cured to yield residue-free, silicone adhesives with improved removal property. The effect in reducing the % haze was observed at as low as 1 part by weight additive per 100 parts by weight solid of the base composition in Example 6. Table III below shows the properties of these compositions.
TABLE III
__________________________________________________________________________
Weight Release
Release
Experiment
Viscosity
Parts
SiH/SiV
Percent
Probe Tack
Peel (Steel)
at 90° %
at 180° %
Number
of Modifier
Additive
Ratio
MQ gms/cm.sup.2
oz/in Haze Haze
__________________________________________________________________________
12 100 M cps
0.99 1.3 57.4 686 37 6.1 2.2
13 100 M cps
2.8 1.3 56.4 636 26 1.8 1
14 100 M cps
5.6 1.3 54.9 644 22 4.4 0.2
__________________________________________________________________________
The effects of the partial miscibility of the release modifier with the base composition of MQ resin, silicone fluids and/or polymers and Pt-catalyst is shown in these Examples 15 and 16. The effectiveness of the modifier in reducing the % haze or surface distortion associated with removal or dispensing is greatly reduced without at least partial miscibility. In Example 15, a dimethylhydroxy-stopped fluorosilicone polymer of 100,000 cps viscosity was used at 5.6 parts by weight per 100 parts by weight of the base composition. In Example 16, a vinyl-stopped copolymer of dimethyl silicone and trifluoropropylmethylsilicone of 29,000 cps was used at 5.6 parts by weight per 100 parts by weight of the base composition. The % haze of 90° angle peeled tapes had readings of 9.4 and 12.5, respectively. The higher % haze in Example 16 was the result of less chemical miscibility with the base material before cure.
Although the present invention has been described in connection with preferred embodiments, it will be appreciated by those skilled in the art that additions, modifications, substitutions and deletions not specifically described may be made without departing from the spirit and scope of the invention defined in the appended claims.
Claims (9)
1. A pressure sensitive adhesive, having improved control removal properties, said adhesive comprising a resin/organopolysiloxane composition curable to produce a pressure sensitive adhesive said organopolysiloxane composition curable to produce a pressure sensitive adhesive comprising about 50 to about 75 parts by weight of a benzene toluene-soluble siloxane resin, about 25 to about 50 parts by weight of vinyl-and hydride-containing organopolysiloxanes, a Pt catalyst, and from 0 to about 40 weight percent organic solvent and from about 0.5 to about 15 weight percent based upon the resin/organopolysiloxane composition of a chemically compatible high molecular weight organopolysiloxane having the general formula:
RR.sup.1.sub.x SiO(R.sup.1.sub.2 SiO).sub.x (RR.sup.2 SiO).sub.y SiR.sup.1.sub.2 R (1)
wherein each R1 is independently an alkyl or aryl group having from 1 to about 10 carbon atoms, each R2 is independently an alkyl or aryl group having from 1 to about 10 carbon atoms, each R is independently chosen from R1 or R2, x is an integer, and y is an integer, x and y having values such that the chain-length dependent viscosity of the chemically compatible high molecular weight polyorganosiloxane is at least 1500 cps at 25° C.
2. A pressure sensitive adhesive as in claim 1, wherein said chemically compatible high molecular weight organopolysiloxane is present in an amount of between 2 and 10 weight percent.
3. A pressure sensitive adhesive as in claim 1, wherein x and y are such that the chain-length dependent viscosity of said chemically compatible high molecular weight organopolysiloxane is at least 7600 cps at 25° C.
4. A pressure sensitive adhesive as in claim 1, wherein x and y are such that the chain-length dependent viscosity of said chemically compatible high molecular weight organopolysiloxane is at least 10,000 cps at 25° C.
5. A pressure sensitive adhesive as in claim 1, wherein x and y are such that the chain-length dependent viscosity of said chemically compatible high molecular weight organopolysiloxane is at least about 85,000 cps at 25° C.
6. A pressure sensitive adhesive as in claim 1, wherein said chemically compatible high molecular weight organopolysiloxane comprises an alkyl-terminated silicone polymer.
7. A pressure sensitive adhesive as in claim 6, wherein said chemically compatible high molecular weight organopolysiloxane comprises a polydimethylsiloxane.
8. A pressure sensitive adhesive as in claim 7, wherein said polydimethylsiloxane has a viscosity of from about 7600 cps to about 8,600,000 cps at room temperature.
9. A pressure sensitive adhesive as in claim 6, wherein said alkyl-terminated silicone polymer is present in an amount of between 2 parts by weight and 10 parts by weight based on 100 parts by weight of the organopolysiloxane composition curable to produce a pressure sensitive adhesive.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/828,437 US5248716A (en) | 1992-01-30 | 1992-01-30 | Silicone pressure-sensitive adhesives with control removal property |
| TW081103643A TW202478B (en) | 1992-01-30 | 1992-05-11 | |
| CA002085643A CA2085643A1 (en) | 1992-01-30 | 1992-12-17 | Silicone pressure-sensitive adhesives with control removal property |
| AU31840/93A AU3184093A (en) | 1992-01-30 | 1993-01-15 | Silicone pressure-sensitive adhesives with control removal property |
| EP93300331A EP0553983B1 (en) | 1992-01-30 | 1993-01-19 | Pressure-sensitive silicone adhesives |
| DE69302184T DE69302184T2 (en) | 1992-01-30 | 1993-01-19 | Pressure sensitive adhesives based on silicone |
| JP01213593A JP3545433B2 (en) | 1992-01-30 | 1993-01-28 | Silicone pressure-sensitive adhesive with controlled release properties |
| KR1019930001132A KR930016518A (en) | 1992-01-30 | 1993-01-29 | Deregulating silicone pressure sensitive adhesive |
| CN93100648A CN1074923A (en) | 1992-01-30 | 1993-01-30 | Silicone pressure sensitive adhesive with control stripping performance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/828,437 US5248716A (en) | 1992-01-30 | 1992-01-30 | Silicone pressure-sensitive adhesives with control removal property |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5248716A true US5248716A (en) | 1993-09-28 |
Family
ID=25251805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/828,437 Expired - Lifetime US5248716A (en) | 1992-01-30 | 1992-01-30 | Silicone pressure-sensitive adhesives with control removal property |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5248716A (en) |
| EP (1) | EP0553983B1 (en) |
| JP (1) | JP3545433B2 (en) |
| KR (1) | KR930016518A (en) |
| CN (1) | CN1074923A (en) |
| AU (1) | AU3184093A (en) |
| CA (1) | CA2085643A1 (en) |
| DE (1) | DE69302184T2 (en) |
| TW (1) | TW202478B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5378406A (en) * | 1992-07-24 | 1995-01-03 | Toshiba Silicone Co., Ltd. | Fungiresistant polyorganosiloxane composition |
| US5436303A (en) * | 1992-01-21 | 1995-07-25 | General Electric Company | Fluorosilicone pressure sensitive adhesives |
| US5747551A (en) * | 1994-12-05 | 1998-05-05 | Acheson Industries, Inc. | UV curable pressure sensitive adhesive composition |
| US20030165676A1 (en) * | 2001-12-18 | 2003-09-04 | Zhiming Zhou | Silicone priming compositions, articles, and methods |
| US6703120B1 (en) | 1999-05-05 | 2004-03-09 | 3M Innovative Properties Company | Silicone adhesives, articles, and methods |
| US6730397B2 (en) | 2001-12-18 | 2004-05-04 | 3M Innovative Properties Company | Silicone pressure sensitive adhesives, articles and methods |
| US20050282024A1 (en) * | 2001-12-18 | 2005-12-22 | 3M Innovative Properties Company | Silicone pressure sensitive adhesives prepared using processing aids, articles, and methods |
| US20080193749A1 (en) * | 2007-02-13 | 2008-08-14 | Thompson D Scott | Molded optical articles and methods of making same |
| US20080203415A1 (en) * | 2007-02-13 | 2008-08-28 | 3M Innovative Properties Company | Led devices having lenses and methods of making same |
| WO2013153501A1 (en) * | 2012-04-09 | 2013-10-17 | Tyco Electronics (Shanghai) Co. Ltd. | Silicone rubber sealing glue used in medium and high voltage cable accessories and cable accessories |
| US20210392968A1 (en) * | 2020-06-20 | 2021-12-23 | Stephen Gerard Fearing | Face mask with adhesive elastic tape fasten |
| US20220411684A1 (en) * | 2019-12-23 | 2022-12-29 | Nissan Chemical Corporation | Adhesive composition, laminate and method for producing same, method for peeling laminate, and method for processing semiconductor-forming substrate |
| US11926765B2 (en) | 2018-11-19 | 2024-03-12 | Nissan Chemical Corporation | Adhesive composition for peeling off by irradiation with light, layered product, and production method and peeling method for layered product |
| US12163049B2 (en) | 2019-09-26 | 2024-12-10 | Dow Silicones Corporation | Silicone release coating composition and methods for the preparation and use of same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4414653A1 (en) * | 1993-05-13 | 1994-11-17 | Gen Electric | Fast Adhesive Silicone Adhesive Compositions |
| DE4414982A1 (en) * | 1993-05-13 | 1994-11-17 | Gen Electric | Silicone pressure-sensitive adhesive compositions |
| KR100377243B1 (en) * | 2000-09-04 | 2003-03-26 | 안택진 | Adhesive composition, tape and label easily peeled off after an extended time period |
| US7056584B2 (en) * | 2002-10-11 | 2006-06-06 | General Electric Company | Bond layer for coatings on plastic substrates |
| JP4619710B2 (en) * | 2004-07-02 | 2011-01-26 | 東レ・ダウコーニング株式会社 | Silicone pressure sensitive adhesive and adhesive tape |
| KR101053839B1 (en) * | 2011-01-28 | 2011-08-05 | 주식회사 오에스아이 | Silicone optical transparent adhesive film with reworkability and excellent transmittance |
| EP2978795B1 (en) * | 2013-03-28 | 2017-05-31 | Dow Corning Corporation | Organosiloxane compositions and coatings, manufactured articles, methods and uses |
| CN110157374A (en) * | 2018-03-26 | 2019-08-23 | 昆山普瑞凯纳米技术有限公司 | A kind of organic pressure-sensitive gel and preparation method thereof |
| CN109207086B (en) * | 2018-09-28 | 2021-10-22 | 张家港康得新光电材料有限公司 | Protective film |
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- 1992-01-30 US US07/828,437 patent/US5248716A/en not_active Expired - Lifetime
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- 1992-12-17 CA CA002085643A patent/CA2085643A1/en not_active Abandoned
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- 1993-01-15 AU AU31840/93A patent/AU3184093A/en not_active Abandoned
- 1993-01-19 EP EP93300331A patent/EP0553983B1/en not_active Expired - Lifetime
- 1993-01-19 DE DE69302184T patent/DE69302184T2/en not_active Expired - Fee Related
- 1993-01-28 JP JP01213593A patent/JP3545433B2/en not_active Expired - Fee Related
- 1993-01-29 KR KR1019930001132A patent/KR930016518A/en not_active Application Discontinuation
- 1993-01-30 CN CN93100648A patent/CN1074923A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5436303A (en) * | 1992-01-21 | 1995-07-25 | General Electric Company | Fluorosilicone pressure sensitive adhesives |
| US5378406A (en) * | 1992-07-24 | 1995-01-03 | Toshiba Silicone Co., Ltd. | Fungiresistant polyorganosiloxane composition |
| US5747551A (en) * | 1994-12-05 | 1998-05-05 | Acheson Industries, Inc. | UV curable pressure sensitive adhesive composition |
| US6703120B1 (en) | 1999-05-05 | 2004-03-09 | 3M Innovative Properties Company | Silicone adhesives, articles, and methods |
| US7090922B2 (en) | 2001-12-18 | 2006-08-15 | 3M Innovative Properties Company | Silicone priming compositions, articles, and methods |
| US7695818B2 (en) | 2001-12-18 | 2010-04-13 | 3M Innovative Properties Company | Silicone pressure sensitive adhesives prepared using processing aids, articles, and methods |
| US20050282024A1 (en) * | 2001-12-18 | 2005-12-22 | 3M Innovative Properties Company | Silicone pressure sensitive adhesives prepared using processing aids, articles, and methods |
| US7012110B2 (en) | 2001-12-18 | 2006-03-14 | 3M Innovative Properties Company | Silicone pressure sensitive adhesives prepared using processing aids, articles, and methods |
| US20030165676A1 (en) * | 2001-12-18 | 2003-09-04 | Zhiming Zhou | Silicone priming compositions, articles, and methods |
| US6730397B2 (en) | 2001-12-18 | 2004-05-04 | 3M Innovative Properties Company | Silicone pressure sensitive adhesives, articles and methods |
| US20080203415A1 (en) * | 2007-02-13 | 2008-08-28 | 3M Innovative Properties Company | Led devices having lenses and methods of making same |
| US20080193749A1 (en) * | 2007-02-13 | 2008-08-14 | Thompson D Scott | Molded optical articles and methods of making same |
| US8330176B2 (en) | 2007-02-13 | 2012-12-11 | 3M Innovative Properties Company | LED devices having lenses and methods of making same |
| US9944031B2 (en) | 2007-02-13 | 2018-04-17 | 3M Innovative Properties Company | Molded optical articles and methods of making same |
| WO2013153501A1 (en) * | 2012-04-09 | 2013-10-17 | Tyco Electronics (Shanghai) Co. Ltd. | Silicone rubber sealing glue used in medium and high voltage cable accessories and cable accessories |
| US11926765B2 (en) | 2018-11-19 | 2024-03-12 | Nissan Chemical Corporation | Adhesive composition for peeling off by irradiation with light, layered product, and production method and peeling method for layered product |
| US12163049B2 (en) | 2019-09-26 | 2024-12-10 | Dow Silicones Corporation | Silicone release coating composition and methods for the preparation and use of same |
| US20220411684A1 (en) * | 2019-12-23 | 2022-12-29 | Nissan Chemical Corporation | Adhesive composition, laminate and method for producing same, method for peeling laminate, and method for processing semiconductor-forming substrate |
| US20210392968A1 (en) * | 2020-06-20 | 2021-12-23 | Stephen Gerard Fearing | Face mask with adhesive elastic tape fasten |
Also Published As
| Publication number | Publication date |
|---|---|
| KR930016518A (en) | 1993-08-26 |
| JPH05345887A (en) | 1993-12-27 |
| CA2085643A1 (en) | 1993-07-31 |
| EP0553983A1 (en) | 1993-08-04 |
| DE69302184D1 (en) | 1996-05-23 |
| CN1074923A (en) | 1993-08-04 |
| DE69302184T2 (en) | 1996-11-28 |
| TW202478B (en) | 1993-03-21 |
| JP3545433B2 (en) | 2004-07-21 |
| EP0553983B1 (en) | 1996-04-17 |
| AU3184093A (en) | 1993-08-05 |
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